目的：建立用N-丙基乙二胺（PSA）净化，液相色谱-三重四极杆串联质谱联用法（LC-MS/MS）测定菊花药材中12种有机磷等多类农药残留的方法，并对产于6个省的4个规格的28批菊花样品进行农药残留测定，对菊花使用的安全性进行评价。方法：菊花样品加乙腈、活性炭和氧化铝提取，过PSA柱净化，采用LC-MS/MS方法在多反应监测（MRM）模式下测定，以磷酸三苯酯为内标进行定量分析。结果：12种农药成分在相应的测定范围内线性关系良好，相关系数在0.9961~0.9999内，12种农药在0.018、0.06、0.18 mg·kg-1 3个添加水平下，加标回收率范围为68.9%~120.4%，RSD（n=3、6、3）范围为1.4%~7.7%，各农药的检出限和定量限分别在0.05~4.1 μg·kg-1和0.2~18.4 μg·kg-1之间；28批菊花样品共检出了多菌灵、吡虫啉、毒死蜱等8种农药残留，但均符合标准规定。结论：该方法经方法学验证可应用于菊花药材中甲胺磷、多菌灵、敌百虫、吡虫啉、敌敌畏、甲霜灵、三唑酮、二嗪磷、甲拌磷、辛硫磷、毒死蜱、氟啶脲12种农药残留的同时检测。
Objective: To develop a method based on PSA-LC-MS/MS for the determination of 12 kinds of pesticide residues in crude drug Chrysanthemi Flos,and to quantify 28 lots of Chrysanthemi Flos of four specifications produced in 6 provinces for the evaluation of safety usage of Chrysanthemi Flos. Methods: Chrysanthemi Flos samples were extracted with acetonitrile,active carbon and aluminum oxide,and purified using a small column of N-propylethylenediamine(PSA).The prepared samples were analyzed by LC-MS/MS in a multiple reaction monitoring(MRM) mode,and the pesticides were quantified by triphenylphosphat internal standard method. Results: All the 12 pesticides showed good linearity in their reasonable ranges (r=0.9961-0.9999).The average recoveries of all the pesticides at three spiked levels of 0.018,0.06 and 0.18 mg·kg-1 were in the range of 70.3%-96.2%,72.4%-120.4% and 68.9%-118.5%;the RSDs(n=3,6,3) were 2.4%-7.7%,3.5%-5.9%,and 1.4%-6.6%,respectively;and the LOD and LOQ were all in the range of 0.05-4.1 μg·kg-1 and 0.2-18.4 μg·kg-1,respectively. Totally 8 kinds of pesticide residues,namely methamidophos,carbendazim,imidacloprid,dichlorvos,metalaxy,triadimefon,phoxim,and chlorpyrifos,were detected in 28 lots of Chrysanthemi Flos samples,and conformed to safety standards. Conclusion: The methodology validation shows that the method is suitable for simultaneous multi-residues analysis of 12 kinds of pesticides in Chrysanthemi Flos,such as methamidophos,carbendazim,trichlorfon,imidacloprid,dichlorvos,metalaxyl,triadimefon,diazinon,phorate,phoxim,chlorpyrifos,and chlorfluazuron.
